Resinous adhesive materials



United States atent O] RESINOUS ADHESIVE MATERIALS James H. Saunders,Anniston, Ala., assignor to Monsanto Chemical Company, St. Louis, Mo., acorporation of Delaware No Drawing. Application June 29, 1953 Serial No.364,930

Claims. (Cl. 260-775) This invention relates to new, resinous materials,and particularly to suitable resins for use as adhesives.

According to the present invention, new, resinous materials are preparedby condensing a compound having the structure:

where X is 0, S or NH and R is selected from the group consisting of NHand:

with a glycol and a triamine, the proportions of the three ingredientsbeing as described hereinafter.

Compounds having the structure:

and useful in the present invention are: urea, thiourea, guanidine,biruet and thiobiniet.

The glycol component employed in the present condensation may be anyglycol, such, for example, as ethylene glycol, propylene glycol,butylene glycol, 2-rnethylbutane diol-2,4,2-ethylhexane dial-1,3,hexamethylene glycol, styrene glycol, N-phenyl diethanolamine, catechol,resorcinol, 2,2-bis(4-hydroxy phenyl) propane, p,p-dihydroxy biphenyl,decamethylene glycol, polyglycol (ethyl glycols) such as polyethyleneglycols, diethylene'glycol, triethylene glycol, tetraethylene glycol,polyethylene glycols having molecular weights of 200, 400 and 600 orintermediate values thereof, polypropylene glycols, polypropylenegylcols having molecular weights of the order of 400, 750, 1200 and2000, monoethers of tri'nydroxy compounds such as glycerine, alpha-allylether, glycerol alpha-phenyl ether, glycerol alpha-isopropyl ether,hydroxy esters such as an ester prepared from one mole of dibasic acidand two moles of a glycol or polyglycol, a polyester prepared so thatthe molar ratio of glycol or polyglycol to the dibasic acid is between 2and 1, an ester prepared from one mole of the dimer acid andZ moles of aglycol or polyglycol, an ester prepared from a hydroxy acid and a glycolor polyglycol so that the molar ratio of the glycol or polyglycol to thehydroxy acid is between 0.5 and 1 and .an ester prepared from one moleof a trihydroxy compound and one mole of a monobasic acid such as themonoglyceride of eleostearic acid.

The triamine component employed in the preparation of of the presentresinous bodies may be any aliphatic or aromatic triamine. In the caseof aromatic triamines the amino groups are preferably attached to thedifierent aromatic nuclei. In the case of aliphatic triamines for bestresults the amino groups should be separated by at least 3 atoms.

Suitable triamines are: 4,4',4-triaminotriphenylmethane,2,4,4"-triaminotriphenylmethane, 2,4-bis-aminobenzylaniline,triaminotritolylmethane, 2,4,4-triaminobi- 2,824,856 Patented Feb. 25,1958 mflc 1,4,S-triaminonaphthalene, 1,3,8-triaminonaph- 1,3,5-triaminobenzene, 1,3,5 -triaminotoluene,

triaminanthracene, tri- Moles of X=C-NH Active hydrogen groupsat least0.25 but not in excess of 1.5

Moles of triarnine moles of glycol =at least 0.25 but, not inexoessof4;0

The active hydrogen atoms employed in the first ratio above are thosefound to be active by the recognized Zerewitinofi method. Thus, a glycolhas two active hy-' drogen groups, and a triamine has three such goups.

The reacting ingredients proportioned in accordance with the abovedirections are introduced into a reaction vessel which is provided witha heating means and facilities for stirring the reacting mass. Thereaction may be carried out in the presence or in the absence of asolvent. When a solvent is employed it may be any suitable highboilingorganic liquid which is a solvent'for the reactants. in the event thatthe solvent so chosen is a non-solvent for the resinous materialsproduced by the condensation, the method utilizing such non-solvent isnot necessarily rendered inoperative. 'In this event, the resinousmaterials at a certain stage in the condensation separate out as 'asecond liquid phase and may be separated by suitable phase separationmethods. Suitable solvents in which the reaction can be carried out maybe any of the following: Chlorinated biphenyls, chlorinatednaphthalenes, di rnethylformarnide, diethylene glycol dimethyl ether,triethylene glycol dirnethyl ether, diethyl phthalate, pyridine,triethylamine, N-methyl morpholine.

' The present reaction may be carried out at temperatures which rangefrom about C. to about 225 C. According to my observations the reactionbetween the ingredients starts at about 90 C. and progresses smoothly asthe temperature is raised to the higher limit. A basic gas, identified'as ammonia, is liberated from the reaction mass commencing at about 90and becoming more rapid at about C.

The temperature and time of treatment employed for the condensation ofthe reactants will vary with the specific ingredients employed in theprocess and will not necessarily be the same for the several alternativematerials included herein. The degree of condensation as measured by themelting point or solubility of theresinone product will depend upon thetime and temperature of heating, in general these properties increasingwith the intensity of heating or the duration of heat treatment. Theresinous compositions are generally insoluble in most solvents and inwater; however, dimethylformamide is a suitable solvent for theseresins, should solutions be de 17.5 grams (0.061 mole) ofp,p',p"-triaminotriphenylmethane, 9 g. of urea (0.15 mole) and 20 g. ofpolythat it couldnotbe pulled apart readily;

" ;In the following series of tests the triamine, urea and and heatedfor an hour at 110-1501 C at which tem i my. Upon further heating at1509' Offer s the remainder also became hard.

V up in such fashioh that theycould be tested in tension and fingresultswere .No.4. Q 5 Components of bonded' st 7 thestructure'withsto at failure. The present res1 ethylene glycol (0.05mole) were .mixed together in i a glass flask and heated on a water-bathat 90-95 C.

7 was placed on an aluminum surface and squeezedbetween 10 anotheraluminum surface. Upon cooling, the bond between the two aluminumobjectsgwasstrong enou'ghfso Example 2 5 glycol were varied so as togive varying values for-the 7 ratios explained above. The followingexperiments were carried out:

.TTA 1 Urea PEG 1 Em m r No. 5 G Ajctiveli g. moles g. moles g. molest'ITA=trtarninotripheriylmethafil it I PE G=polyethylene p Moleratio. L75 V 7 Ratio of moles of urea to total equivalents of active H groups. 7o

The above ingredients weremixed in -2-ounce bottles glycol, 400 M. W.

peratures the compositions were hom0geneons,i thin liquids.- 5 Uponcooling to room temperature, experiment 5 was hard, while the otherswere very: syrupy and gum- V everal hours, Theresin produced inexperiment N materials together. To this end test samples were made 7 ameasure-of strength of the hond obtained. The follow ructure: p. 54. atfailure 1 Steel/resin/steel 575 5 Steel/resin/glassMagnesium/resin/magnesiumV .Steel/resin/vinyl plastic- 1 20 In.a;sirnilar manner the resin in-experiment No. 5 was' employed to jointwo aluminum she'ets- Up on testing,

nous products may be employed to adhesively bond various structuralelementstogether; such I ';for example, as wood to wood, glass to'glass,fiber board to fiber hoard, cloth to cloth, paper to paper, regenerated.60

' prising the follo 5 7 said mixture being such as to 'satisfy theratio: 7

' Moles of 'triamine 7 I V Moles of' glycol V n I I b ,4 i th ab v 40 .52. The condensation producfd'efined. in.claim"fl in' f 5 tabulationwasemployed in cementing various structural i ,which the compound:

obtained .with the resin of experiment is urea. ,1

od a stress of more than: 1250 p. s. i. '55? steel to glass, steel toaluminum, steel to cellulose acetate,

' steel to acrylic plastics, steel to vinyl plastics, .;steel towood, asheet of .metal foilto a moisture-proof material comprising a'cellulos'ic mate .5 What I'claim is:-

1. The resinous condens ing to a temperature of at least (3.; amixturecom.-

wing reactants-: (1').a compound of the formula:

NH and R is selec t2) aglycol and (3) a triamine, said triamine'containing; 7 only NH groups and no other; active hydrogen contain-'-'ing groups, the relative proportions of said reactants in Moles X=o-NH,.7 Active hydrogen groups? relative prop ratio:

at 50.25 but 555'. 111 885.55 1.5

which the glycol-is polyethyleneglycol. V i

3.,The condensation product defined in claim l,

Y. N n i V v 4. T he, condensation product defined 1115151811 1 whichthe triamine 'is triaminotriphenylmethane, p; r

5. The condensation product defined in claim 1, in thylene glycolhavinga molecuwhich the glycol is a polye lar weight of abou 40Q. V 5 55e e 1 V 7 References Cited file of this patent; UNITED SIATES PATENTS2,145,242 p 2,155,328 =Paquin Apr. 18, 939 5 FOREIGN PATENTS; L Franceune .2, 1942} e rial and various cornbinations" 5 of these and otherbases. V 5

ation product. obtained by heat-' V 25 but not in excess. of inwhich'ratio the active. hydrogen groups gajrejtheuactive hydrogen groupspresentin saidiglycol-and 'triamine, the

ortions of said reactantsalso satisfyingthe fini U. S. DEPARTMENT OFCOMMERCE PATENT OFFICE CERTIFICATE 0F CQRRECTION February 25, 1958Patent Noo 2,824.,856 Jemee Swmziere It is hereby certified that errorappears .in the printed specification of the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

@olumn 2 line 38 f0]: "excess of 105" read. ==excese of 400 Signei andsealed; day of June 1958,

(SEAL) Atfiest:

KARL Ho K ZLINE ROBERT C. WATSON Comissioner of Patents AttestingOfficer

1. THE RESINOUS CONDENSATION PRODUCT OBTAINED BY HEATING TO ATEMPERATURE OF AT LEAST 90*C., A MIXTURE COMPRISING THE FOLLOWINGREACTANTS: (1) A COMPOUND OF THE FORMULA: